Studies on the emission behavior of polypropylene by gas chromatography/mass spectrometry with static headspace or thermodesorption

Emissions from polypropylene (PP) may cause undesired smell, be harmful, or lead to so-called fogging which prohibits its use for car interiors. Thus, qualitative as well as quantitative emission studies are necessary. Thermodesorption (TDS) and static headspace (sHS) with subsequent GC-MS analysis are two powerful tools for analyzing the emission behavior of polymers with a minimum of sample handling. In this work we investigated the emission behavior of PP with TDS and sHS coupled to GC-MS paying special attention to quantitative considerations and to the relevance of emitted substances for fogging phenomena. After extraction for 30min and incubation for 2h, TDS-GC-MS and sHS-GC-MS results were satisfyingly repeatable (with relative standard deviations up to 5%). TDS allowed to introduce substances up to higher boiling points into the GC-MS system, but required to control sample geometry, as emission depended rather on sample surface than on sample mass. In sHS, emission was governed by partitioning between the gas and the sample phase rather than by full evaporation of the analytes. Above a certain analyte-dependent amount, peak area became independent of the sample amount. However, if the sample amount was kept constant, peak areas of emitted substances showed a linear dependence upon concentration of volatiles. Therefore, accurate quantitation was still possible. Typically alkanes, alkenes and dialkenes dominate TDS-GC-MS and sHS-GC-MS chromatograms of PP. They only contributed to fogging if they had a chain length higher than C16. These substances were only detectable when TDS was used for sample introduction, but not with sHS. sHS-GC-MS is thus not useful for judging fogging behavior.     

A new transmission method in dielectric time domain spectroscopy

A new transmission TDS method for permittivity measurements using the linear dependence of the attenuation coefficient and the phase coefficient with sample length is described. Experimental results for methanol in carbontetrachloride at room temperature are reported.     

Quantitative aspects of the desorption of copper from the silicon (100) surface

The desorption of copper from copper contaminated Si(100) samples has been investigated by thermal desorption spectroscopy (TDS). The samples have been contaminated with aqueous CuSO(4)/EDTA solutions. The amount of copper deposited on the Si surface was in the monolayer region as determined by means of ratio-tracer experiments. The copper is adsorbed on the sample surface in two different states, which could be resolved by TDS. By means of STM and XPS measurements it was possible to assign these two desorption peaks to the desorption of copper from carbon deposits, which had already been present before the contamination process, and to the desorption of copper from the bare Si surface.     

Quantitative aspects of the desorption of copper from the silicon (100) surface

The desorption of copper from copper contaminated Si(100) samples has been investigated by thermal desorption spectroscopy (TDS). The samples have been contaminated with aqueous CuSO₄/EDTA solutions. The amount of copper deposited on the Si surface was in the monolayer region as determined by means of ratio-tracer experiments. The copper is adsorbed on the sample surface in two different states, which could be resolved by TDS. By means of STM and XPS measurements it was possible to assign these two desorption peaks to the desorption of copper from carbon deposits, which had already been present before the contamination process, and to the desorption of copper from the bare Si surface.     

Optimisation of stir bar sorptive extraction for the analysis of volatile phenols in wines

An easy, fast and reliable analytical method is proposed for the determination of the concentration of volatile phenols (ethyl- and vinylphenols) in wines. The novel stir bar sorptive extraction (SBSE) technique is employed, following a simple and fast procedure that allows 15 samples to be extracted simultaneously using very small sample volume. Extracts are desorbed in a thermodesorption system (TDS) coupled on-line to a gas chromatograph-mass spectrometry system. The SBSE offers better recovery and linear regression coefficient (r2) for the four volatile phenols than solid-phase extraction (SPE). The mass spectrometric detection in selected ion monitoring mode contributes to the lower detection limit and good sensibility obtained with this method.     

Sampling variability and uncertainty in total diet studies

Here, the uncertainty budget for a total diet study (TDS) was clarified by separating the total measurement uncertainty into the uncertainty arising from the compositional heterogeneity of food items between cities (referred to as inter-city variance), the heterogeneity of food items within cities (intra-city variance), and the chemical analysis of the food samples (analytical variance) at one study design. TDS samples were collected from 14 cities in Japan. Duplicate samples collected in each city were prepared from food items purchased from different shops, and the cadmium concentrations were measured individually to obtain the intra-city variance. These results were used to show the importance of sampling design in TDSs, by evaluating a sampling method known as a multi-stage design, in which multiple samples are collected from several cities. Such schemes have been applied to TDSs, but the uncertainty involved has not been assessed. An intra-city correlation was observed between the cadmium concentrations in samples from the same city, demonstrating that the effective sample size was not simply the number of cities and shops sampled. The TDS results showed a high intra-city variance, which was greater than the inter-city variance for all of the food groups studied, and particularly for the bean and potato groups. By combining the sampling and analytical uncertainties obtained, the sampling uncertainty across different primary sampling unit sizes and secondary sampling unit sizes was obtained. As suggested by the analysis of potatoes and beans, grouping food samples from different shops in the same city can improve the representativeness of the results.     

In vitro percutaneous absorption of thiamine disulfide through rat skin from a mixture of propylene glycol and fatty acid or its analog.

Percutaneous absorption of thiamine disulfide, (TDS), a lipophilic derivative of thiamine, from a mixture of propylene glycol (PG) and fatty acid (FA) or its analog through rat skin was tested in vitro. Lauric acid (12:0) enhanced the absorption depending on its concentration in PG and showed a maximal enhancement at 10% w/w. At 10% w/v, lauryl alcohol also enhanced the absorption, but less than 12:0, which lauric acid methyl ester suppressed the absorption. The flux of TDS did not depend on the solubility of TDS in the vehicle, but on the permeability coefficient. From these results, it is suggested that FA increases the permeability coefficient not only because FA increases TDS diffusion by disrupting lipid packing in the stratum corneum but also, FA increases TDS partition to lipid phase by interacting with TDS.     

Adsorption of water on JSC‐1A (simulated moon dust samples)—a surface science study

JSC‐1a (a simulated lunar dust sample) supported on a silica wafer (SiO₂/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x‐ray (EDX) spectroscopy, and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and in addition by collecting isothermal adsorption transients. Blind experiments on the silica support have been performed as well. JSC‐1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg, as characterized in detail in prior studies, for example, at NASA. The particle sizes span the range from a few micrometers up to 100 µm. At small exposures, H₂O TDS is characterized by broad (100–450) K structures; at large exposures, distinct TDS peaks emerge, which are assigned to amorphous solid water (ASW) (145 K) and crystalline ice (CI) (165 K). Water dissociates on JSC‐1a at small exposures but not on the bare silica support. Coadsorption TDS data (alkane–water mixtures) indicate that rather porous condensed ice layers form at large exposures, with the mineral particles acting most likely as nucleation sites. At thermal impact energies, the initial adsorption probability amounts to 0.92 ± 0.05. It is evident that the drop‐and‐dry technique, developed in studies about nanoparticles/tubes, can be extended to obtain samples for surface science studies based on powders consisting of particles with rather large diameters. Copyright © 2008 John Wiley & Sons, Ltd.     

Numerical study of a drug release profile in the transdermal drug delivery system

Drug release by diffusion from an unstressed thin polymer film with a dissolved crystallizable component was simulated using a kinetic Monte Carlo model. This model was used previously to study Ostwald ripening in a high crystallizable component regime and was shown to correctly simulate solvation, diffusion, and precipitation. In this study, the same model with modifications was applied to the drug transportation and release in the low concentration regime of interest to the transdermal drug delivery system (TDS) community. We demonstrate the model's utility by simulating diffusion, crystal precipitation, growth and shrinkage during storage, and drug release from the thin TDS to a surface under different conditions. The simulation results provide a first approximation for the drug release profile occurring from TDS to skin. It has been reported that growth of drug crystals in TDS occurs mainly in the middle third of the polymer layer at relatively higher temperatures. The results from the simulations showed that the release rate and concentration profile of a TDS depend on the dissolution process of the crystal. At low storage temperature, the drug precipitates to form small evenly distributed crystals throughout the thickness of the TDS patch. The release rate of these small, evenly distributed crystals most closely matched that of a completely dissolved drug.     

Determination of benzothiazole in untreated wastewater using polar-phase stir bar sorptive extraction and gas chromatography-mass spectrometry

Stir bar sorptive extraction (SBSE) was applied to extract benzothiazole (BT) from untreated wastewater using a novel polyacrylate (PA)-coated stir bar (PA Twister^®). After extraction, BT was desorbed in a thermal desorption system (TDS) and analysed by GC–MS (gas chromatography–mass spectrometry). The sample contained 30% (w/w) NaCl, the sample temperature was 30 °C and the extraction time was 240 min. Since no filtering or clean-up steps or solvents were necessary SBSE clearly performs better than all previously used extractions techniques for analysing BT in untreated wastewater in terms of easy use, sample throughput and analytical costs. In addition, matrix effects were small. The calibration curve resulting from the standard addition method was linear with a value of the stability index (R²) of 0.999 (n = 3). A good inter-day repeatability of the method was observed with a relative standard deviation (RSD) of 9.8% (n = 6). A low limit of detection (LOD) of 0.256 μg L⁻¹ was achieved using only a small sample volume of 18 mL. Small sample volumes significantly reduce sample transport costs. The concentration of BT in untreated wastewater was determined to be 1.04 μg L⁻¹.     

Preconcentration of trace metals from salt solutions using thiuram disulphide as collector

Traces of Fe, Co, Ni, Cu, Zn, Cd and Pb in salt solutions (e.g. KCl, Ca(NO₃)₂, A1₂(SO₄)₃, Cr₂(SO₄)₃, (NH₄)₂SO₄) are determined by flame AAS after preconcentration with thiuram disulphide (TDS) as collector precipitate. The preconcentration recovery is mainly influenced by pH, TDS amount and its aging in the sample solution. Conditions of an optimal preconcentration procedure were elaborated. Detection limits vary from 0.5 ng/ml (for Cd) to 8.3 ng/ml (for Pb) and the relative standard deviation is 2 to 6 %. The accuracy of the results was checked by differential pulse anodic stripping voltammetry and by electrothermal AAS.     

Simultaneous determination of tandospirone and its active metabolite, 1‐[2‐pyrimidyl]‐piperazine in rat plasma by LC–MS/MS and its application to a pharmacokinetic study

A rapid, sensitive and selective liquid chromatography–tandem mass spectrometry method for the detection of tandospirone (TDS) and its active metabolite 1‐[2‐pyrimidyl]‐piperazine (1‐PP) in Sprague–Dawley rat plasma is described. It was employed in a pharmacokinetic study. These analytes and the internal standards were extracted from plasma using protein precipitation with acetonitrile, then separated on a CAPCELL PAK ADME C₁₈ column using a mobile phase of acetonitrile and 5 mm ammonium formate acidified with formic acid (0.1%, v/v) at a total flow rate of 0.4 mL/min. The detection was performed with a tandem mass spectrometer equipped with an electrospray ionization source. The method was validated to quantify the concentration ranges of 1.000–500.0 ng/mL for TDS and 10.00–500.0 ng/mL for 1‐PP. Total time for each chromatograph was 3.0 min. The intra‐day precision was between 1.42 and 6.69% and the accuracy ranged from 95.74 to 110.18% for all analytes. Inter‐day precision and accuracy ranged from 2.47 to 6.02% and from 98.37 to 105.62%, respectively. The lower limits of quantification were 1.000 ng/mL for TDS and 10.00 ng/mL for 1‐PP. This method provided a fast, sensitive and selective analytical tool for quantification of tandospirone and its metabolite 1‐PP in plasma necessary for the pharmacokinetic investigation.     

Fenugreek mucilage as a flocculating agent for sewage treatment

The use of fenugreek mucilage, a natural polysaccharide and a direct food additive, as a flocculating agent for removal of suspended and dissolved solids from sewage effluent has been reported. A flocculation study has been done by the standard jar test method. The percent removal of suspended solid (SS) and dissolved solid (TDS) was determined by varying the polymer dose, pH and contact time. X-ray diffraction patterns of the solid waste material of mucilage and flocs (so obtained after treatment) were used to suggest the incorporation of the crystalline waste material in the mucilage. The optimal mucilage concentration was found to be 0.16 mg/l. The suitable pH range for maximum solid removal (SS and TDS) was alkaline and the time required for treatment was 1-3 h.     

高性能和强扩展性的太赫兹时域光谱仪的研制

太赫兹波具有低能、宽带和独特的时域脉冲特性等特点,使其在材料物质科学领域具有着重要的应用价值.自主搭建了一套基于光电导天线的太赫兹时域光谱仪.从介绍光电导天线产生和探测太赫兹波的原理出发,重点阐述了太赫兹时域光谱仪的光路设计优化、搭建调试、功能拓展和应用实例分析,为自主研制高性能太赫兹时域光谱仪提供了方法和经验.     

Profiling of trace elemental impurities in caustic soda matrix by inductively coupled plasma mass spectrometric technique

An inductively coupled plasma mass spectrometric (ICP-MS) technique method is developed for simultaneous determination of Li, Cr, Mn, Fe, Ni, Co, Cu, Sr, Ag, Cd, Ba, and Pb at trace level in caustic soda. Operational parameters of the instrument were optimized and suitable accessory (argon gas dilution) was used in the method. Direct aspiration of high total dissolved solids (TDS) samples (beyond 0.2% TDS) and highly alkaline NaOH is not suitable for the instrument; therefore, strategy of neutralization of NaOH by HNO₃ was adopted to handle its high alkalinity. Suitable internal standards of low, mid, and high atomic masses were used with external calibration. Features such as matrix matching, calibration verification, interference correction, etc. were undertaken in this work. Neutralized caustic soda samples were spiked with the analytes with lower, middle, and higher concentration. The results of spiking with 30, 70, 140, and 200 ppb were examined. The method exhibited excellent accuracy and precision.     

Simultaneous determination of major to ultratrace elements in geological samples by fusion-dissolution and inductively coupled plasma mass spectrometry techniques

A method has been developed for the simultaneous quantification of major to ultratrace elements in geological samples using quadrupole ICP-MS techniques. The sample preparation involves fusion with LiBO₂ and dilution in HNO₃-HF which allows complete decomposition of refractory minerals and quantification of the elements of interest. The effects of high Total Dissolved Solids (TDS) and Li in the solution are minimized using a matrix-tolerant interface and conditioning the instrument with LiBO₂ solution. The signal drift is moreover controlled using conventional internal standards and specific Drift Correction Standards (DCS). A key issue of the technique is the external calibration using selected Certified Reference Materials (CRM). Depending on the sample type and analytes of interest three optimized programmable modes are used sequentially: Standard, Collision Cell (CCT) and Kinetic Energy Discrimination (KED) mode. The method allows to quantify more than 40 elements in concentrations from tens-of-percent to <0.1 ppm levels during a single experiment. The method has been validated through the analysis of different CRMs with recovery factors of ca. 100% and typical 2σ errors of <10%.     

PLANTAGO PSYLLIUM-GRAFTED-POLYACRYLONITRILE： SYNTHESIS,CHARACTERIZATION AND ITS USE FOR SOLID REMOVAL FROM SEWAGE WASTEWATER

Plantago psyllium mucilage (PSY), an anionic natural polysaccharide consisting of pentosan and uronic acid obtained from the seeds of Plantago psyllium (Plantago family), was grafted with acrylonitrile (AN). Graft copolymers were prepared by ceric ion initiated solution polymerization technique and were characterized by FT-IR spectroscopy, scanning electron microscopy and differential scanning calorimetry. These copolymers are good flocculating agents for removal of suspended (SS) and total dissolved solid (TDS) in sewage wastewater treatment. The effects of copolymer dose, pH and contact time on flocculation capacity of one selected copolymer sample were studied by jar test method. The suitable pH range for maximum solid removal was 7.0 to 9.2 and the optimum copolymer dose was 1.2mg/L. The overall process for solid removal took 4h. X-ray diffraction (XRD) patterns of grafted copolymer, PSY grafted polyacrylonitrile (PSY-g-PAN) and solid waste, before and after treatment are used to suggest the interaction of the solid waste with PSY-g-PAN copolymer.     

Thermal desorption of hydrogen from carbon nanosheets

Carbon nanosheets are a unique nanostructure that, at their thinnest configuration, approach a single freestanding graphene sheet. Temperature desorption spectroscopy (TDS) has shown that the hydrogen adsorption and incorporation during growth of the nanosheets by radio frequency plasma-enhanced chemical vapor deposition are significant. A numerical peak fitting to the desorption spectra (300-1273 K) via the Polanyi-Wigner equation showed that desorption followed a second order process, presumably by the Langmuir-Hinshelwood mechanism. Six peaks provide the best fit to the TDS spectra. Surface desorption activation energies were determined to be 0.59, 0.63, and 0.65 eV for the external graphite surface layers and 0.85, 1.15, and 1.73 eV for desorption and diffusion from the bulk. In contrast to TDS data from previously studied a-C:H films [Schenk et al. J. Appl. Phys. 77, 2462 (1995)], a greater amount of hydrogen bound as sp(2) hybridized carbon was observed. A previous x-ray diffraction study of these films has shown a significant graphitic character with a crystallite dimension of L(a)=10.7 nm. This result is consistent with experimental results by Raman spectroscopy that show as-grown carbon nanosheets to be crystalline as commercial graphite with a crystallite size of L(a)=11 nm. Following TDS, Raman data indicate that the average crystallite increased in size to L(a)=15 nm.     

Determination of calcium, magnesium, sodium, and potassium in foodstuffs by using a microsampling flame atomic absorption spectrometric method after closed-vessel microwave digestion: method validation

This paper describes a validation process in compliance with the NFIEN ISO/IEC 17025 standard for the determination of the macrominerals calcium, magnesium, sodium, and potassium in foodstuffs by microsampling with flame atomic absorption spectrometry after closed-vessel microwave digestion. The French Standards Commission (Agence Francaise de Normalisation) standards NF V03-110, NF EN V03-115, and XP T-90-210 were used to evaluate this method. The method was validated in the context of an analysis of the 1322 food samples of the second French Total Diet Study (TDS). Several performance criteria (linearity, LOQ, specificity, trueness, precision under repeatability conditions, and intermediate precision reproducibility) were evaluated. Furthermore, the method was monitored by several internal quality controls. The LOQ values obtained (25, 5, 8.3, and 8.3 mg/kg for Ca, Mg, Na, and K, respectively) were in compliance with the needs of the TDS. The method provided accurate results as demonstrated by a repeatability CV (CVr) of < 7% and a reproducibility CV (CVR) of < 12% for all the elements. Therefore, the results indicated that this method could be used in the laboratory for the routine determination of these four elements in foodstuffs with acceptable analytical performance.     

Comparative in vivo constituents and pharmacokinetic study in rats after oral administration of ultrafine granular powder and traditional decoction slices of Chinese Salvia

Salvia miltiorrhiza, one of the most well‐known herbal medicines, is commonly used for the treatment of coronary heart diseases in China. Besides traditional decoction slices (TDS), another relatively new product of S. miltiorrhiza, ultrafine granular powder (UGP; D90 < 45 μm), is also increasingly being used. In this paper, a UHPLC‐LTQ‐Orbitrap MS technique was developed for a metabolite profile study after oral administration of UGP and TDS of S. miltiorrhiza. The results showed that the number of in vivo absorbed compounds from UGP was much greater than that from TDS, and different types of products from S. miltiorrhiza will have different metabolic processes in vivo. Furthermore, a UHPLC‐Q‐Trap MS/MS method for simultaneously determining four tanshinones (tanshinone IIA, dihydrotanshinone I, tanshinone I and cryptotanshinone) was established and applied to assess the pharmacokinetics of the two types of products. All of the analytes displayed significant higher area under the concentration–time curve and peak concentration after oral administration of UGP than after TDS, indicating that ultrafine powder product could improve the bioavailability and absorption of cryptotanshinon,tanshinone II A,dihydrotanshinonE I and tanshinone I in vivo. The present study provides scientific information for further exploration of the pharmacology of these two types of S. miltiorrhiza and offers a reference for clinical administration of S. miltiorrhiza.